Water-soluble dyestuffs



United States Patent fl ,540 WATER-SOLUBLE DYE'STUFFS Max Staeuble,Basel, and Kurt Weber, Bottmingen,

Switzerland, assignors to Ciba Limited, Basel, Switzerland No Drawing.Claims prioritz',

Filed Dec. 5, 1958, Ser. No. 778,277 application Switzerland Dec. 16,1957 Claims. (Cl. 260-328) v This invention provides water-solubledyestuifs which contain at least one group imparting solubility in waterand an aliphatic halogen-acyl radical, especiallyan aliphatichalogen-acyl radical of low molecular weight, bound through a nitrogenbridge and containing at least one halogen atom, for example, a chlorineatom, advantageously in the ii-position and also containingaheterocyclic 6-membered ring which is fusedon each side to an aromaticnucleus and which contains a keto group and as the sole heteroatom asulfur or nitrogen atom in para-position to the keto group.

As halogenated acyl radicals there may be mentioned radicals ofaliphatic halogen-carboxylic acids, advantageously saturatedhalogen-carboxylic acids '(for'example, fi-chloropropionic acid), andalso halogenated acyl radicals of aliphatic halogen-sulfinic or-sulfonic acids, for example, chlorethane sulfonic acid.

The invention also provides a process for the manufacture of theaforesaid dyestuifs, wherein an advantageously water-soluble dyestutfwhich contains an acylatable amino group and a heterocyclic G-m'embered'ring which is fused on each side to an aromatic nucleus and contains asthe sole heteroatom a sulfur or nitrogen atom in paraposition to a ketogroup, is acylated at the acylatable amino group with an anhydride orhalide of a halogenat least one acid group strongly imparting solubilityin water, such as a carboxyl group or preferably a sulfonic acid group.7

Accordingly, the dyestuffs used as starting material contain theskeleton of the formula 7 in which R and R each represent an aromaticradical fused on to the heterocyclic ring at the positions indicated bythe valency bonds, the aromatic radical being advantageously of thebenzene or naphthalene series, and X represents a sulfuratom, which maybe hexavalent as, for example'in the -SO:- group, or a nitro-:

gen atom. Inthese dyestulfs the acylatable, that is to say primary orsecondary, amino group and, if desired,

other substituents, may be present in an external nucleus that is tosay, in a nucleus which is bound to one of the radicals R and R throughan oxygen'atomthrough ad- 2,989,540 Patented June 20, 19 61 CO orSO;-.--.- group, through acarboxylic acid amide grouping, through as-ulfonic .acid amide girouporadva n tageouslyothrough an --Nl-Irgroup." As dyestuffs con taining an acylatable amino group bound inan external nucleus there may be mentioned aminophenylarrfinmacriLclones and thioxanthone's. It is of advantage touse dye.- stulfs of thistype which contain a group imparting solubility in water in the externalnucleus, if the radicals Ri and R contain no such groups. Instead ofbeing presen't in an external nucleus, the reactive amino group may bebound directly. or through an -SO2--. group, or through analkyleneradicahto one of the radicals R and R As starting materialsthere may be mentioned, for example, those of the formula I s I Hols inwhich Y represents an -SO group or an -NH-' group, and especiallythioxanthone dyestuffs, such as thje aminothioxanthone'sulfonic acids ofthe formula j QIS I HO;

and

and also the corresponding thiox'anthone-S-d ioxides;"

The starting materials used in the process of this invention can also beobtained, for example, by reacting a sulfonic acid halide of an acridoneor thioxanthone dyestuff (such as is obtainable, for example, bytreating the dyestuif with chlorosulfonic acid or by reacting thedyestufi sul-fonic acid with an acid-halogenating agent, such aphosphorus halide, thionyl chloride or chloro'sulionic acid) with anorganic compound which contains an acylatable group, especially anacylatable amino group, and contains, in addition to the saidac'yla'table group, an acylatabl'e amino group or a substituentconvertible into such a group after the react-ion with the dyestufisulfonic acid halide. As suchor g'anic compounds there are thereforeused bifunctionally organic compounds such as diamines, for example,cyclic, and especially aromatic, diai'nines such as 4:4'-diarninophenyl,4:4-diair'1iriostilbene-2:2-disulfonic acid, l':4- oi-1:3-di'air'iinobenie'ne and especially 1:4-diaminobenzene-Z-suIfonic'acid and lz3-diaminobenzene-4-sulfonic acid. There may also be usednitranilines or monoacyl-derivatives of organic 'diamines, in whichcase, after the reaction with the dyestufi sulfonic acid chlorideused,an additional free amino group is formed by reduction or hydrolysis. Inselecting the starting materials care must be taken that the productobtained contains at least one acylatable amino group and at least onecarboxylic acid or sulfonic acid group. Accordingly, there is used asstarting material a dyeism containing at least one sulfonic acidhalidegroup and it is reacted with a dia'inine containing a carboxylic acidandlo'r sulfonic acid group. If the 'dianiir'le contains no sulfonicacid group, it must be reacted with not more than one sul'fonic acidhalide group of a dyestuff sulfonic acid halide of the kind definedabove containing at least two such groups. p p

The acylation of the dyestuffs defined above containing an acylatablegroup with the anhydride or halide of an aliphatichalogen-carboxylicacid or halogen-sulfonic acid in the process of this invention isadvantageously carried out in the presence of an acid-binding agent suchas sodium acetate, sodium hydroxide or sodium carbonate, and underconditions such that the final product still contains the exchangeablealiphatically bound halogen atom, that is to say, for example, in anorganic solvent or at a relatively low temperature in an aqueous medium.

The dyestuffs so obtained are preferably isolated at a low temperature,for example, by salting out and filtration or by evaporation of thereaction mixture. The isolated dyestufi's are dried, if desired, afterthe addition of an extender, and drying is preferably carried out at nottoo high a temperature and under reduced pressure. By spray drying thewhole reaction mixture it is in some cases possible to obtain drypreparations directly, that is to say, without intermediate isolation ofthe dyestuffs. By these methods valuable new dry preparations areobtained, which are sutiable for preparing stock solutions or dyebathsahd, if desired, printing pastes.

The new dyestufis of this invention are useful for dyeing or printing avery wide variety of materials, such as superpolyamide fibers, andespecially p'olyhydroxylated fibrous materials which may be eithersynthetic, for example, of regenerated cellulose, or natural materials,for example, cellulose, linen or especially cotton. They are suitablefor dyeing by the so-called direct dyeing, method from aqueous alkalinebaths, which may contain a high concentration 'of a salt, and areespecially suitable for dyeing by printing or pad-dyeing methods, inwhich the dye'stiifi "is applied to the "material to be dyed by printingor padding, and fixed on the material by means of an acid-binding agent.

The dyeings produced on cellulos'ic fibers with the new dyestuffs areusually distinguished by the purity of their tints, by their goodfastness to light and above all by their excellent fastness to washing.7

The following examples illustrate the invention, the parts andpercentages being by weight:

EXAMPLE 1 O NH:

- sonar 3.5 parts of the sodium salt of lz4-diaminothioxanthone sulfonicacid are dissolved in 100 parts of water and a solution of 2 parts ofp-chloropropionyl chloride in 4 parts of toluene is added at 0-2 C.while stirring well. The mineral acid split off during the acylation iscontinually neutralized at 0-4" C. with a l N-solution of sodiumhydroxide so as to maintain the pH value of the solution between 5.0 and7.0. When the reaction has finished and no more acid splits oil, the'pH-value ofth'e solution is adjusted to 8.5 by the further addition ofsodium hydroxide solution. The dyestutf is then salted out from solutionwith sodium chloride, filtered 0E, and dried in "vacuo at -80 C.

The dyestufi so obtained dyes cotton and regenerated cellulose by thedyeing prescription given below greenish yellow tints of very goodfastness to washing. The lz4-diamino-thioxanthone sulfonic acid isobtained from l:4-'diamincrthioxanthone by heating the latter for onehour 'with 10 times its weight of oleum containing 5% of at -100 C.

By using, instead of 2 parts of chloropropionyl chloride, thecorresponding quantity of chlorethane sulfonic solution. The impregnatedfabric is dried, then impregnated a't room temperature with a solutioncontaining, per liter, 10 grams of sodium hydroxide and 300 grams ofsodium chloride, and the material is squeezed to a weight increase of75% and steamed at -101 C. for 4 minutes. The fabric is then rinsed,treated in a sodium bicarbonate solution of 0.5% strength, rinsed,soaped at the boil for A hour in a solution of 0.3% strength of a nonionic detergent, rinsed and dried. There is obtained a yellow dyeingwhich is fixed fast to boiling.

EXAMPLE 2 SOsH (I? NH c 4.2 parts of the sodium salt of1-phenylamino-4-aminothioxanthone sulfonic acid are dissolved in partsof water and acylated at 0-4 C. with 2 parts of p-chloropropionylchloride by the method described in Example 1 and isolated.

In the dry state the dyestutf is a yellow powder which i dyes cotton andregenerated cellulose by the dyeing prescription given in Example 1yellow tints of very good fastness to washing and light. Alternatively,the dyeing may be carried out in accordance with the dyeing prescriptiongiven below.

The -1-.phenylamino-4-amino-thioxanthone sulfonic acid used in thisexample is obtained by heating l-ph'enyl- Dyeing prescription 2 parts ofthe dyestufi of the formula given in this example and 1 part of a 10n-solution of sodium hydroxide are dissolved in 25 parts of urea and 75parts of water. A cotton fabric is impregnated in the solution, and thensqueezed to a weight increase of 75% and dried. After being heated for60 seconds at 160 C. the fabric is rinsed and soaped. There is obtaineda yellow dyeing which is fast to boiling.

[ AMPLE 3 v H NHCgHs scan 1 1 111-0 o-om cl 3.7 parts of the sodium saltof l-ethylamino-4-aminothioxanthone sulfonic acid aredissolved in 100parts of water and 2 parts of chlor-acetyl chloride are added at 4 C.while stirring well. The mineral acid split off during the acylation isneutralized at 04 C. with a dilute solution of sodium hydroxide so as tomaintain the pH-value of the solution between 5.0 and 7.0. When thereaction is finished and no more acid splits 01f, the

dyestufl? is salted out with sodium chloride, filtered off and dried at70 C. in vacuo.

Cotton and regenerated cellulose are dyed by the dyeing prescriptiongiven in Example 2 orange-yellow tints of very good fastness to washing.

The 1-ethylamino-taminmthioxanthone sulfonic acid used in this exampleis obtained from l-ethylamino-4- amino-thioxanthone by heating thelatter for one hour in six times its weight of oleum of 8% SO -contentat 90- EXAMPLE 4 4 parts of the sodium salt of1-anilino-4-amino-acridone sulfonic acid are dissolved in 200 parts ofwater, and acylated at 02 C. with 2 parts of fl-chloropropionylchloride, while stirring, in the manner described in Example 1 andisolated.

There is obtained in the dry state a yellow-brown dyestuff powder, whichdyes cotton and regenerated cellulose by the dyeing prescription givenin Example 1 yellow tints of very good fastness to washing.

The -1-anilino-4-amino-acridone sulfonic acid used in this example isobtained by reducing 1-anilino-4-nitroacridone to1-anilino-4-amino-acridone and then sulfonating the latter with sulfuricacid of 100% strength at 90- EXAMPLE 5 5 parts of a. so'lutionof thesodium salt of 1-( 4-aminophenylamino) 4 nitroj .thioxanthone-S-dioxidesulfonic acid of the probable formula; r

soul I .:N01 in 100 parts of water are aeylated at 074 C. with 2 partsof p-chloro'propionyl chloride, while ,stirring vigorously, by themethod described in; Example 1 and the product is isolated. I i

There is obtained a dyestuif which dyes cotton and regenerated celluloseby the method described in Example l violet-grey tints of Very goodfastness to washing. j

The 1-(4-aminophenylarnino) 4 nitro-thiozanthone- S-dioxide sulfonicacid used in this example may be prepared as follows:

l-chloro-4 nitro-thioxanthone is oxidized in glacial acetic acid withhydrogen peroxide to form 1 chloro-4- v'nitro.-thioxanthone-S-dioxide,and the latter is then condensed in boiling nitrobenzene with1:4-diaminobenzene to form1-(.4.-aminopheny1amino)-4-nitro-thioxanthone- S-dioxide. The product issulfonated by treatment with oleum containing 10% of 50;, at 130-135 C.

EXAMPLE 6 4.2 parts of the sodium salt ofl-phenylamino-4-aminothioxanthone sulfonic acid of the probable formulaQ II are dissolved in 200 parts of water. The solution is cooled to 05C. and 3.3 parts of anhydrous sodium acetate are first added, whilestirring, and then a solution of 2.7 parts of chloromaleic acidanhydride in 10 parts of acetone is added, and the whole is stirreduntil acylation of the amino group is complete. The mixture is thenadjusted to a pH-value of 9 by the addition of sodium carbonate, and thedyestufi formed is salted out with sodium chloride, filtered ofi? anddried in vacuo at 70-75 C.

The dyestufi so obtained dyes cotton by the method described in Example1 yellow tints of very good fastness to light and washing.

EXAMPLE 7 NH-Q-O on.

UG 803E 4.5 parts of the sodium salt of1-(4'-methoxyphenylamino)-4-amino-thioxanthone sulfonic acid aredissolved in parts of water and acylated at 0-2 C. with a solution of 2parts of 2-chloropropionyl chloride in 4 parts of toluene, whilestirring, by the method described in Example 1, and the product isisolated.

Cotton and regenerated cellulose are dyed with the re- 7 sultingdyestufi by the method described in Example 1 orange-yellow tints havinga very good fastness to washing and light. t The 1 (4'methoxyphenylamino)-4-amino-thioxanthone sulfonic acid used in thisexample can be prepared as follows: 1-chloro-4-nitro-thioxanthone iscondensed in boiling paraanisidine to form1-(4'-methoxyphenylamino)-4-nitro-thioxanthone, and the latter isconverted by reducing the nitro group by a customary method, forexample, by catalytic hydrogenation with Raney nickel, into1-(4-methoxyphenylamino)-4-aminothioxanthone. The amino-derivative, issulfonated by heating it with 10 times its weight of sulfuric acid of100% strength for a short time at 120-130 C., and isolating the 1-(4'methoxyphenylamino)-4-amino-thioxanthone sulfonic acid by pouring thesulfonation mixture into sodium chloride solution of 10% strength.

What is claimed is:

1. The thioxanthone dyestufi of the formula II C R NHCOCHzCH2Cl whereinR represents the sulfonic acid group.

3. The dyestufi which in its free acid state corresponds to the formula4. The dyestuff which in its free acid state corresponds to the formulaOOH:

Amstrutz et 81.: Journal of the American Chemical Society, vol. 69,pages 1927 and 1929 (1947).

Archer et al.: Journal of the American Chemical Society, vol. 47, pages4300 and 4305 (1952).

1. THE THIOZANTHONE DYESTUFF OF THE FORMULA